CN107282110A - A kind of ethylene oligomerisation catalyst composition and application - Google Patents

A kind of ethylene oligomerisation catalyst composition and application Download PDF

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CN107282110A
CN107282110A CN201610195750.8A CN201610195750A CN107282110A CN 107282110 A CN107282110 A CN 107282110A CN 201610195750 A CN201610195750 A CN 201610195750A CN 107282110 A CN107282110 A CN 107282110A
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compound
ethylene oligomerization
alkoxy
reaction
alkyl
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CN107282110B (en
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吴红飞
郑明芳
祁彦平
刘珺
王霄青
韩春卉
栗同林
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
    • B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
    • B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/226—Sulfur, e.g. thiocarbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
    • C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
    • C07C2/08—Catalytic processes
    • C07C2/14—Catalytic processes with inorganic acids; with salts or anhydrides of acids
    • C07C2/20—Acids of halogen; Salts thereof ; Complexes thereof with organic compounds
    • C07C2/22—Metal halides; Complexes thereof with organic compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/20—Olefin oligomerisation or telomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
    • B01J2531/62—Chromium
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2531/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • C07C2531/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • C07C2531/22—Organic complexes

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

This application discloses a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including ligand compound shown in Formulas I, transistion metal compound, containing aluminum cocatalyst, TBHP and organic solvent；Wherein, X is O or S；R1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkyl, alkoxy or halogen.Present invention also offers a kind of ethylene oligomerization method, it is included in the presence of above-mentioned ethylene oligomerization carbon monoxide-olefin polymeric, carries out ethylene oligomerization reaction.The carbon monoxide-olefin polymeric provided according to the present invention, the active high, advantage that selectivity is high.

Description

A kind of ethylene oligomerisation catalyst composition and application
Technical field
The present invention relates to ethylene oligomerization field, and in particular to a kind of catalyst for ethylene oligomerization reaction process Composition, the present invention is also accordingly related to a kind of ethylene oligomerization method.
Background technology
Ethylene oligomerization be olefinic polymerization industry in it is most important reaction one of., can will be cheap by oligomerisation reaction Small-numerator olefin be transformed into high value-added product.Ethylene oligomerization product-linear alpha-alkene (LAO) It is important Organic Chemicals.Such as LAO C4-C8It is main as important Organic Ingredients and chemical intermediate To be applied to production high-quality polyethylene (PE) field.By 1- hexenes or 1- octenes and ethylene copolymer produce it is linear Low density polyethylene (LDPE) (LLDPE) can significantly improve PE properties, particularly can significantly improve the machine of polyethylene Tool performance, optical property and tear strength and impact strength, product are very suitable for packaging film and greenhouse, canopy The fields such as the agricultural mulch films such as room.LAO C10-C30Can be used as preparing daily cleaning agent, flotation agent, emulsifying agent, It is the emollient component and bore liquid emollient component of refrigeration machine, plasticizer, various additives, low sticky artificial oil, poly- It is compound and copolymer, oil and oil product additive, senior alkylamines, senior organo-aluminum compound, senior Additive of alkaryl hydrocarbon, higher aliphatic and aliphatic acid, epoxides and heat carrier etc.. LAO C20-C30On the basis of can also composite adhesives, sealant and coating.In recent years, with polyolefin industry Continue to develop, to the demand rapid development of alpha-olefin in world wide.Wherein most alpha-olefins is Prepare what is obtained by ethylene oligomerization.
Since the seventies in last century, the research of transient metal complex catalysis in olefine polymerization and oligomerisation gradually by To the attention of scientist, people start to make great efforts research raw catelyst and improve existing catalyst, improve catalyst The selectivity of activity and catalysate.In numerous explorations, research is earliest, with fastest developing speed, compare concentration It is nickel cation type catalyst system and catalyzing, the United States Patent (USP) such as reported already has US3686351 and US3676523, And Shell Co. Ltd's SHOP techniques based on the patented technology.It is related in Shell Co. Ltd's SHOP techniques O-P bridging type parts, but contain virose organophosphorous groups in the catalyst, and synthesis step is complicated, steady It is qualitative poor.Developed many patents such as O-O, P-N, P-P and N-N type coordination Raney nickel again later, Such as JP11060627, WO9923096, WO991550, CN1401666, CN1769270 etc..However, The relatively complicated shortcoming of the catalyst generally existing preparation method that is obtained by above-mentioned patent.Other catalyst are also There are chromium system, zirconium system and aluminium system etc., Brookhart groups (Brookhart, M et al., J.Am.Chem.Soc., 1998,120,7143-7144；WO99/02472,1999), Gibson groups (Gibson, V.C. et al., Chem. Commun.,1998,849-850；Chem.Eur.J., 2000,2221-2231) find respectively some Fe (II) and Co (II) trident pyridinimine complex can be catalyzed ethylene oligomerization, and not only the catalytic activity of catalyst is very high, and And the selectivity of alpha-olefin is also very high.As the co-catalyst of ethylene oligomerization, either MAO, still Modified methylaluminoxane, all has that cost is too high, and the problem of consumption is excessive is used as co-catalyst large-scale application When ethylene oligomerization, it certainly will cause production cost high.
Today, it is generally accepted that water and oxygen are very unfavorable to ethylene oligomerization reaction process, it has been disclosed that ethene it is neat Poly- method, is strict controlled in progress in the environment of anhydrous and oxygen-free, therefore current ethylene oligomerization reaction will to technique Ask very harsh, cause the reaction of oligomerisation reaction technique to trigger and repeated all excessively poor.
The content of the invention
The present inventor is neat in research heterocyclic ethene in order to overcome the shortcoming and deficiency of above-mentioned catalyst During poly- catalyst, it has surprisingly been found that ethene including the catalyst ligand shown in Formulas I, transistion metal compound, Carbon monoxide-olefin polymeric effect containing aluminum cocatalyst and TBHP is lower to carry out oligomerisation reaction, has on the contrary Significantly higher oligomerisation reaction activity, and oligomerisation reaction trigger it is rapid, operate steadily, it is reproducible；The tert-butyl group Hydrogen peroxide promotes the progress of reaction, so as to overcome those skilled in the art's as organic peroxide Technology prejudice, achieves unexpected technique effect.
Therefore, there is provided a kind of ethylene oligomerization carbon monoxide-olefin polymeric in first embodiment of the present invention, Including the ligand compound shown in Formulas I, transistion metal compound, containing aluminum cocatalyst and TBHP；
Wherein, X is O or S；R1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkane Base, alkoxy and halogen.
In a preferred embodiment of the present invention, the alkyl is C1-C20Alkyl, preferably C1-C10 Alkyl, more preferably C1-C6Alkyl.The alkyl in the present invention includes at least one of following group： It is methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, secondary Amyl group, isopentyl, n-hexyl, Sec-Hexyl, isohesyl, n-heptyl and its isomers, still more preferably first Base, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, sec-butyl, the tert-butyl group, n-pentyl, secondary penta Base, isopentyl, n-hexyl or isohesyl；Most preferable, ethyl, n-propyl, isopropyl, normal-butyl or Isobutyl group.
In a preferred embodiment of the present invention, the alkoxy is C1-C20Alkoxy, preferably C1- C10Alkoxy, more preferably C1-C6Alkoxy.The alkoxy in the present invention is included in following group It is at least one：Methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, isobutoxy, Zhong Ding Epoxide, tert-butoxy, n-pentyloxy, secondary amoxy, isoamoxy, positive hexyloxy, secondary hexyloxy, dissident Epoxide, positive epoxide in heptan and its isomers；Still more preferably methoxyl group, ethyoxyl, positive propoxy, isopropyl oxygen Base, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, secondary amoxy, isoamyl oxygen Base, positive hexyloxy or dissident's epoxide；Most preferably methoxyl group, ethyoxyl, positive propoxy, isopropoxy, positive fourth Epoxide or isobutoxy.
In a preferred embodiment of the present invention, the halogen is selected from fluorine, chlorine or bromine.
In a preferred embodiment of the present invention, the transistion metal compound be selected from chromium, molybdenum, iron, titanium, At least one of compound of zirconium and nickel, preferably is selected from chromium trichloride, chromium acetylacetonate, isooctyl acid chromium and three (four At least one of hydrogen furans) chromium trichloride.
In a preferred embodiment of the present invention, the co-catalyst is organo-aluminum compound；It is preferred that alkyl At least one of aluminium compound and/or aluminium alkoxide compound, more preferably following compound：Trimethyl aluminium, three second Base aluminium, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, aluminium diethyl monochloride, ethyl aluminum dichloride, first Base aikyiaiurnirsoxan beta, ethylaluminoxane or modified methylaluminoxane；Most preferably MAO or triethyl aluminum.
In a preferred embodiment of the present invention, the part, transistion metal compound and co-catalyst Mol ratio is 1：(0.1-10)：(1-1000), preferably 1：(0.25-2)：(10-700), it is more excellent Elect 1 as：(0.5-2)：(100-500).And in the transition metal and co-catalyst in transistion metal compound The mol ratio of metal be preferably 1:(50-1000).Within the above range, be conducive to obtaining higher active urge Agent composition.
In a preferred embodiment of the present invention, organic solvent is also included in the composition.Wherein, Using the weight of organic solvent as calculating benchmark, the weight of the TBHP contained in the carbon monoxide-olefin polymeric Amount content is 25-1000ppm；More preferably 150-750ppm, most preferably 250-500ppm.In above-mentioned model In enclosing, higher catalytic activity can be obtained.
In a preferred embodiment of the present invention, the organic solvent is selected from arene compounds and aliphatic hydrocarbon Class compound.The arene compounds preferably be selected from benzene,toluene,xylene, monochlor-benzene, dichlorobenzene, Trichloro-benzene or at least one of monochlorotoluene and its derivative；The aliphatic hydrocarbon compound preferably is selected from straight chain In at least one of alkane, branched paraffin or cycloalkane, more preferably pentane, heptane, hexamethylene or hexane It is at least one.
Second embodiment of the present invention also provides a kind of ethylene oligomerization method, is included in above-mentioned ethylene oligomerization and uses In the presence of carbon monoxide-olefin polymeric, ethylene oligomerization reaction is carried out.
In a preferred embodiment of the present invention, the reaction temperature of the reaction is the C of 0-200 zero, preferably 0-100○C.Wherein, reaction pressure 0.1-6.0MPa, preferably 0.5-5.0MPa.
In a preferred embodiment of the present invention, using the volume of composition as calculating benchmark, the transition gold The concentration for belonging to compound is 0.001-1mmol/L.
Specifically, in the ethylene oligomerization or olefin(e) oligomerization technique of the present invention：By ethene or alkene, optional have Machine solvent and carbon monoxide-olefin polymeric of the present invention are added in reactor, then control ethylene pressure (namely control Reaction pressure processed) it is 0.1-6.0Mpa, preferably 0.5-5.0MPa；Reaction temperature is the C of 0-200 zero, the preferably C of 0-100 zero It is lower to be reacted, after reaction terminates, room temperature is cooled to, takes gas, liquid product to carry out chromatography.At one In specific example, using the volume of composition as calculating benchmark, the concentration of transistion metal compound is 0.001-1mmol metals/L.
The carbon monoxide-olefin polymeric provided according to the present invention, ethene is including the catalyst ligand shown in Formulas I, transition Metallic compound, containing aluminum cocatalyst and the effect of TBHP carbon monoxide-olefin polymeric, lower to carry out oligomerisation anti- Should, with higher oligomerisation reaction activity, and oligomerisation reaction trigger it is rapid, operate steadily, it is reproducible.Urge Change system is relatively simple, it is easy to prepares and is controlled.Ethylene oligomerization reaction is carried out when using the catalyst system When, catalyst activity is high, the C in product6-C18And above constituent content is high, can meet the current world to α-C6、 α-C8、α-C10And the demand of above long-chain olefin product.
In the present invention, especially in the pilot scale and industrial processes of ethylene oligomerization, not only need not strictly it control Anhydrous and oxygen-free system processed, on the contrary, in the presence of organic peroxide-TBHP, having on the contrary Have a higher polymerization activity, and reaction trigger it is rapid, operate steadily, it is reproducible, achieve beneficial Effect.
Embodiment
The present invention is described in detail with reference to embodiments, it will be appreciated that the scope of the present invention is not limited In following examples.
In an embodiment of the present invention, nuclear magnetic resonance uses Bruker companies of Switzerland AV400MHz nuclear magnetic resonance Spectrometer is detected.
Gas-chromatography is detected using the chromatograph of Hewlett-Packard 5890.Mass spectrum uses U.S. Finnigan company's T race DSQ type gas chromatograph-mass spectrometers are detected.
Embodiment 1
Using stainless steel polymeric kettle.Stainless steel polymeric kettle is heated to 100 DEG C, nitrogen displacement number is used after vacuumizing It is secondary, it is then charged with when ethene is 2MPa to ethylene pressure and is down to room temperature.Then toluene is added at 70 DEG C, together When add 5 μm of ol ligand compounds 1 (shown in formula I, wherein X=S, R1=R2=R3=R4=CH3), chlorine Change chromium, TBHP and triethyl aluminum, the cumulative volume of mixed liquor is 100mL, wherein part, chlorination The mol ratio of chromium and MAO is 1：1：200, i.e. chromium chloride addition are that 5 μm of ol, triethyl aluminums add Enter amount for 1mmol；Al/Cr mol ratios are 200.Counted on the basis of the weight of organic solvent, tert-butyl hydroperoxide The weight content of hydrogen is 25ppm.Reaction pressure 2.0MPa is controlled, ethene is passed through, ethylene oligomerization reaction is carried out.
After the completion of reaction, system is cooled to room temperature, gaseous products is collected in aerometer measuring tank, liquid-phase product Collect in conical flask, add 1mL ethanol as terminator, terminate ethylene oligomerization reaction.Liquid phase product meter Measure laggard promoting the circulation of qi analysis of hplc.As a result it is as shown in table 1.
Embodiment 2
Be the same as Example 1, difference is, TBHP content is 150ppm；As a result such as the institute of table 1 Show.
Embodiment 3
Be the same as Example 1, difference is, TBHP content is 300ppm；As a result such as the institute of table 1 Show.
Embodiment 4
Be the same as Example 1, difference is, TBHP content is 500ppm；As a result such as the institute of table 1 Show.
Embodiment 5
Be the same as Example 1, difference is, TBHP content is 750ppm；As a result such as the institute of table 1 Show.
Embodiment 6
Be the same as Example 1, difference is, TBHP content is 1000ppm；As a result such as table 1 It is shown.
Embodiment 7
Be the same as Example 1, difference is, TBHP content is 1500ppm；As a result such as table 1 It is shown.
Embodiment 8
Triethyl aluminum is changed to MAO, other conditions be the same as Example 6；As a result it is as shown in table 1.
Embodiment 9
Al/Cr mol ratios are changed to 50, other conditions be the same as Example 6；As a result it is as shown in table 1.
Embodiment 10
Al/Cr mol ratios are changed to 1000, other conditions be the same as Example 6；As a result it is as shown in table 1.
Embodiment 11
Be the same as Example 6, difference is, using ligand compound 2, the wherein X=O in Formulas I, R1=R2=R3=R4=CH3；As a result it is as shown in table 1.
Embodiment 12
Be the same as Example 6, difference is, using ligand compound 3, the wherein X=S in Formulas I, R1=R2=R3=R4=H；As a result it is as shown in table 1.
Comparative example 1
Be the same as Example 1, difference is that the weight content of TBHP is 0ppm.As a result such as table 1 It is shown.
It can be seen from the data in Table 1 that the carbon monoxide-olefin polymeric provided according to the present invention, ethene is containing the tert-butyl group The carbon monoxide-olefin polymeric effect of hydrogen peroxide is lower to carry out oligomerisation reaction, on the contrary with higher oligomerisation reaction activity, Catalyst activity contrast with comparative example 1 is visible, under the conditions of identical oligomerisation, carbon monoxide-olefin polymeric phase in the present invention The catalyst activity answered will improve several times.And in the obtained selectivity and comparative example of alpha-olefin of the embodiment of the present invention Alpha-olefin selectivity compared to equally all very high.
In addition, in the present invention oligomerisation reaction trigger it is rapid, operate steadily, it is reproducible.Even in Al/Cr ratios When as little as 50, catalyst still has preferable oligomerisation reaction catalytic activity in the present invention, makes ethylene oligomerization anti- Cost is answered to decline to a great extent, its is practical, industrial prospect is wide.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to the present invention's Any limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein used Word is descriptive and explanatory vocabulary, rather than limited vocabulary.Can be by regulation in the claims in the present invention In the range of the present invention is modified, and in without departing substantially from scope and spirit of the present invention to the present invention progress Revision.Although the present invention described in it is related to specific method, material and embodiment, it is not intended that The present invention is limited to wherein disclosed particular case, on the contrary, to can be extended to other all with identical function by the present invention Methods and applications.

Claims (10)

1. a kind of ethylene oligomerization carbon monoxide-olefin polymeric, including ligand compound, transition metal shown in Formulas I Compound, containing aluminum cocatalyst and TBHP；
Wherein, X is O or S；R1、R2、R3And R4It is identical or different, it is each independently selected from hydrogen, alkane Base, alkoxy and halogen.
2. composition according to claim 1, it is characterised in that the alkyl is C1-C20Alkyl, it is excellent Elect C as1-C10Alkyl, more preferably C1-C6Alkyl；And/or the alkoxy is C1-C20Alkoxy, it is excellent Elect C as1-C10Alkoxy, more preferably C1-C6Alkoxy.
3. composition according to claim 1 or 2, it is characterised in that in the composition further Include organic solvent, preferably using the weight of the organic solvent as calculating benchmark, the TBHP Weight content is 25-1500ppm, preferably 150-1000ppm, most preferably 250-750ppm.
4. the composition according to any one of claim 1-3, it is characterised in that the ligand compound： Transistion metal compound：The mol ratio of co-catalyst is 1:(0.1-10):(1-1000), preferably 1:(0.25-2): (10-700), more preferably 1:(0.5-2):(100-500)；And the transition gold in transistion metal compound The mol ratio of metal in category and co-catalyst is more preferably 1:(50-1000).
5. the composition according to any one of claim 1-4, it is characterised in that the transition metal Compound is selected from least one of compound of chromium, molybdenum, iron, titanium, zirconium and nickel, preferably is selected from chromium trichloride, second At least one of acyl acetone chromium, isooctyl acid chromium and three (tetrahydrofuran) chromium trichlorides.
6. the composition according to any one of claim 1-5, it is characterised in that the co-catalyst is Organo-aluminum compound；It is preferred that alkyl aluminum compound and/or aluminium alkoxide compound；In more preferably following compound extremely Few one kind：Trimethyl aluminium, triethyl aluminum, triisobutyl aluminium, tri-n-hexyl aluminum, tri-n-octylaluminium, a chlorine two Aluminium ethide, ethyl aluminum dichloride, MAO, ethylaluminoxane and modified methylaluminoxane.
7. the composition according to any one of claim 3-6, it is characterised in that the organic solvent choosing From arene compounds and aliphatic hydrocarbon compound；The arene compounds preferably be selected from benzene,toluene,xylene, Monochlor-benzene, dichlorobenzene, trichloro-benzene or at least one of monochlorotoluene and its derivative；The aliphatic series Hydrocarbon compound preferably is selected from least one of linear paraffin, branched paraffin and cycloalkane, more preferably pentane, heptan At least one of alkane, hexamethylene and hexane.
8. a kind of ethylene oligomerization method, is included in the ethylene oligomerization according to any one of claim 1-7 and uses In the presence of carbon monoxide-olefin polymeric, ethylene oligomerization reaction is carried out.
9. method according to claim 8, it is characterised in that the reaction temperature of the reaction is 0-200 DEG C, It is preferred that 0-100 DEG C；And/or, reaction pressure 0.1-6.0MPa, preferably 0.5-5.0MPa.
10. the method according to claim 7 or 8, it is characterised in that using the volume of composition as calculating Benchmark, the concentration of the transistion metal compound is 0.001-1mmol/L.
CN201610195750.8A 2016-03-31 2016-03-31 Ethylene oligomerization catalyst composition and application thereof Active CN107282110B (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040147771A1 (en) * 2002-10-25 2004-07-29 Chow Stanley Wai-Yan Polymerization catalyst composition
CN104415787A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040147771A1 (en) * 2002-10-25 2004-07-29 Chow Stanley Wai-Yan Polymerization catalyst composition
CN104415787A (en) * 2013-08-23 2015-03-18 中国石油化工股份有限公司 Olefin polymerization catalyst composition and application method thereof

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